Abstract
Substituted acetonitriles containing an activated methylene group are capable of reacting with ketones in the presence of strong bases [1]. We have found that adamantan-2-one (I) reacts with acetonitrile in the presence of powdered potassium hydroxide and dicyclohexano-18-crown-6 to give 2-adamantylideneacetonitrile (II). Under these conditions, intermediate 2-(2-hydroxy-2-adamantyl)acetonitrile (III) readily undergoes dehydration to nitrile II which is obtained as the major product (up to 90%, according to the GLC data). The dehydration is favored by elimination of steric strain, which accompanies the transition from the sp-hybridized bridging carbon atom in hydroxy nitrile III to sp in II. 2-Adamantylideneacetonitrile (II) was synthesized previously by the Knoevenagel condensation of adamantan-2-one with cyanoacetic acid [2]. Nitrile II characteristically showed in the H NMR spectrum signals from nonequivalent protons in the bridgehead positions neighboring to the double bond ( 2.64 and 3.13 ppm).
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